Reaction product of alkyleneimine with ammonium thiocyanate



Patented May 1945 UNlTED STATES PATENT oFrl'cE REACTION PRODUCT OF ALKYLENEIMINE WITH AMMONIUM THIOCYANATE Roger A. Mathes, Akron, hio, assignor to The B. F. Goodrich Company, corporation of New York New York, N. Y., a

No Drawing. Application June 9, 1943,

- Serial No. 490,220

2 Claims. A (01. 260-583) This invention relates to the reaction products of allgyleneimines with ammonium thiocyanate;

These products, the structure of'which is not definitely known, are useful as accelerators for the vulcanization of rubber, and also as activators for other accelerators, such as the mercaptobenzothiazoles or the .mercaptoalkylthiazoles. Onlysmall amounts of my new products are necessary to achieve the desired results, either as activators or as accelerators. In general, from 0.1 to 5.0% or more, based on the rubber composition, may be used. a

It has been found that alkyleneimines react,

even at room temperature, with ammonium thic-v cyanate with the liberation of ammonia to form products of varying molecular weight, depending upon the amount of alkyleneimine employed. It appears that some sort of polymerization-type reaction occurs if more than one molecular proportion of the alkyleneimine is used for each molecular proportion of ammonium thiocyanate.

It has been found that from one to five or ten or even more molecular proportions of the alkyleneimine may be reacted with one molecular proportion of ammonium thiocyanate. All of these products have closely related chemical proper-- Example I i To a solution of 38 g. of ammonium thiocyanate in 100cc. oi! methanol was added slowly and with stirring over a period of about one-half hour a ture may be heated to the reflux temperature (0. 65 C.) in order to ensure completion of the reaction. The methanol may then be removed by evaporation. There were obtained about 53 g. of a viscous dark-colored syrupv which was practically insoluble in ether, and could not be distilled even at reduced pressure without decom-- position.

Example II To a solution of 19 g. of ammonium thiocyanate in '75. cc. of methanol was added slowly and with stirring a solution of 43 g. of ethyleneimine in- 150 cc. of methanol over a period of about onerose steadily from 23? ,the course of the addihour. The temperature to about 37 C. during vtiori, and a considerable amount of ammonia was evolved. After completion of the addition, the reaction mixture was heated at reflux temperature for about an hour to complete, the reaction. The methanol was then removed by evaporation at reduced pressure, leaving about 5'7 g. of a viscous dark-colored liquid product.

, Example I II About 2.28 g. of ammonium thiocyanate was dissolved in 25 cc. of methanol. To this solution there was added over a period of about 15 minutes ata temperature of about 25 to of 10.32 g. of ethyleneimine in 10 cc. otwater, during which time considerable heat and ammonia gas was evolved. The reaction mixture was then allowed to stand in an open container for several hours at room temperature, and was sub.-

solution of 21.5 g. of ethyleneimine in 100 cc. of

methanol. Stirring was continued for an additional hour, the temperature of the reaction mixture rising from 28 C. at the beginning 01 the addition to as high as 49 C., and ammonia being liberated. Cooling is desirable to prevent the;

temperature'from rising so high that the reaction becomes violent. After about an hour the mixapproximately seven sequently heated at 50 to C. untll'no more weight was lost. About 10.9 g. of a viscous darkcolored product was obtained. indicating that molecular proportions of ethyleneimine had reacted with one of ammonium 'thiocyanate.

Example IV Over a period of about. 15 minutes at a-temperature of 20 to 35 C. there was added to a solution of 2.28 g. or ammonium thiocyanate in 25 cc. oi'methanol a solution of 20.64 g. or ethyleneimine in 20 cc. of .methanol. After the completion of the addition to evaporate several hours at room temperature, and was then warmed until the weight became onstant at 19.4 g., indicating that approximate- C. a solution the mixture was allowed 1y 14 molecular proportions of ethyleneimine had reacted with one of ammonium thiocyanate. The

product was a dark viscous liquid.

As an indication of the accelerating'powe'r'oi these compounds, I shall describe the eil'ect produced in rubber by the product of Example I. The following rubber composition, in which the parts are byweight, was prepared:

Rubber 100 Zinc 5 Laurie ar Sulfur Product of Exampl I. 1

After vulcanization in a press at 287 F. the composition had the p y ical properties shown in the capable of being stored for long periods oftime at room temperature without deterioration.

Although I have described the preparation of these products carried out at room temperature and at atmospheric pressure, higher temperatures and pressures may be employed if desired; however, there appears to be no advantage in em- 'ploying such higher temperature and pressure.

following table, in which T is the ultimate'tensile strength in lb.-sq. in. and E is' the ultimate Equally good results may be obtained using other similar products, prepared as described above.

These new products are quite stable and are In general, it is found that the boiling point of the particular allwleneimlne employed, at atmospheric pressure, is a sufliciently high temperature to ensure completion of the reaction within a reasonable time.

Although I have herein disclosed specific embodiments of my invention, I do not intend to limit myself solely thereto, but only to the extent indicated in the appended claims.

I claim: v l. The product prepared by reacting one molecular proportion of ammonium thiocyanate with at least one molecular proportion of an alkyleneimine, with the liberation of ammonia, at a tein perature below about C.

2. The product prepared by reacting one molecular proportion of ammonium thiocyanate with at least one molecular proportion of ethyleneimine, with the liberation of ammonia, at a temperature below about 70 C. v

' mm a 

